Monoazo dyestuffs



Patented June 9, 1936 UNITED STATES PATENT OFFICE MONOAZO DYESTUFFS Max Schmid, Riehen, near Basel, Switzerland,

assignor to the firm Society of Chemical Industry in Basle, Basel, Switzerland Claims.

in which R1 represents an alkyl or aryl radical, R2 the radical of an aromatic diamine-compound, and R3 an alkyl or aryl radical. These products may also be made by converting the aromatic diamino-compound by condensation with 1 mol. of a c-ketone-carboxylic acid ester into a monoacylated diamine of the formula wherein R2 and R3 have the significance already given, and then converting this monoacylated diamine into the unsymmetrical diacylated derivative required by the invention by condensa tion by means of an acylating agent which contains no COCH2-group capable of coupling.

As aromatic diamino-compounds there may be used, quite generally, aromatic paraand metadiamines, as well as their derivatives; such products are, for example paraand meta-phenylene diamine or toluylenediamine and their nuclear substitution products, for instance the halogen or alkoxy-derivatives; benzidine; tolidine; dianisidine; dichlorobenzidine; products like 4,4'- or 3,3-diamino-diphenylmethane or 4,4'- or 3,3- diarm'no-benzophenone; 4,4-diamino-stilbene; 4,4'- or 3,3-diaminodiphenylurea; 3,3-, 4,4'-, 4,3- or 4',3-diaminobenzanilide; 4,4-diaminodiphenylether or sulfide; 4,4'- or 4,3'-diaminophenoxyacetylaminobenzene, 4,4'-diaminoazobenzene; 4,4-diamino-2-methyl-5-methoxyazobenzene; 4,4'- or 3,3-diamino-azoxybenzene or the like.

As ,B-ketonecarboxylic acid esters there may be used aceto-acetic esters and their analogues, for example benzoyl-acetic esters, or terephthaloylacetic esters; also malonic esters. A

As acylating agents containing no COCHzgroup capable of coupling there may be named acetylating agents, propionylating agents, substituted acylating agents such as phenoxyacetylab ing agents, benzoylating agents, substituted aroylating agents, or the like.

The new, unsymmetrical diacylated derivatives dissolve, in consequence of the presence of the -COCH2COgroups in alkalies and are capable of coupling with diazo-compounds to form azodyestuffs. They have a very good affinity for vegetable fibre as well as for regenerated cellulose,

' so that they may be used with success for producing fast tints on the fibre by the usual icecolor methods. Such methods are, for example, padding the fibre in an alkaline solution of the new arylide and developing with a diazo-compound the fibre thus prepared. The new compounds may also be made into preparations of printing colors which contain an alkali salt of the new asymmetrically acylated derivatives of arcmatic diamino compounds anda diazo-compound stabilized in the form of a nitrosamine or of a diazo-amino-compound. These preparations may be printed on the fibre and then developed into dyestufis by suitable treatment, for example by passage through acid. By another method a mixture of the free diazotizing component or the corresponding N-nitramine and of an alkali salt of the new coupling component may be printed on the fibre and then converted into the dye-stuff by development with nitrous acid and, if desired, by subsequent treatment with alkali. 30

In many cases it is advisable to use the diazocompounds in the form of stable diazo-compounds. There may be applied here the double salts which are obtained by causing the diazocompounds to react with heavy metal salts, such as zinc chloride, or with aromatic sulfonic acids, such as chlorobenzene sulfonic acid, naphthalenemonosulfonic or -disulfonic acid, such as 1,5- naphthalene-disulionic acid, or sulfonic acids of 40 other products, such as, for example, the monoand disulfonic acids of the diphenyl oxide, diphenylene oxide or diphenylene dioxide.

Among the dyestuffs of the present application, which correspond to the general formula itr a-t ai H H 0 o N=N-R4 in which R1 represents an alkyl or aryl radical R2 the radical of an aromatic diamine-compound, R3 an alkyl or aryl radical, and R4 the radical of such a diazo-compound which contains no group promoting solubility, those are particularlyvalu- 7 able whichderive from the arylides of the general II I II II OH HO O already explained, in whichthe radical R2 cor-' responds withthe radical of a diamino -com 7 pound of the diphenyl series, such as benz'idine,

' tolidine or dianisidine, i. e. compounds which be 'long' to the group of the"4,4-diaminodiphenyl compounds. Among the dyestufis of this group those are again particularly valuable in which :the radicalR1 represents the radical of an ali-- I p fi arboxylic acid containing not more than 3 carbon atomsfsuch as for'example the. radical of the propionic acid, of the acetic acidyof th'e V monochloroacetic acid or'i'of the :methoxy acetic acid;

pounds of the benzene, naphthalene'and anthraquinone series which contain no 30311 or COOH groups,- and which have already'ibeen recommended in the iusual' dyeing with ice-colors.

There may of course also be used other 112.20-

fic'ompo unids such asffor examplegtho'se which dev rivelffrom aminoaao c'ompounds' or from heterocyic'lic" compounds, "such i'asaaminocarbazole or a aminodiphenylene"oiiidesl' Among these diazo compoundsithose offthe'benzene sriei 'particularly mononuclear dia'zocompoundsof theiben- Z6116 series, arevaluable; D'ueto their beautiful" shades and other valuable fa stness properesg'the "dyestuffs from "esters V of the 'anthranilic facid are" particular-1 valuable. V

' "The newg unsymmetrical 'diacylated products i f ma'yalso b'e used Iforkmaking: other dyestuffs. 40

Thus they yield in (substance, when'i'c'onibin'ed with the same inon'sulfonat'ed compounds with which they "are used for' nfaki'ng 'fa's't tints on or "for "coloring lacquers; svarnis'hesior the like; with suli'onated "diam-"compounds: they couple to form vw'ool and cotton edyestuffs soluble in 'water. The following examplestillustrate the inven- 'tion"without',howe ver; limiting :its scope, :the partsbeingbyweight:+

"LExamplei :22;6 parts of rnonoace tyl" benzidine; produced ini-known' manner, and 200'parts of xylene are heatedtogether. to' boiling'in a closed apparatus -tered;and heated in-steam-to expel-adhering V g io ;having a-refiux condenser, while stirring. Into 7 V a the feebly boiling massthere aredropped in,'in V: .the course of about half-an-hour, 16 parts of f 'ethylacetoacetate.

Boiling about haLf-an-hour under such conditions that about -100 parts oftxy-lene distil. The whole isthen allowed tocboland the solid-matter-fib' xylene; Iti-is then dissolved in a cold aqueous alcoholic sodium hydroxide solution." IhQjSOlli- 7 tion is filtered and fromthe filtrate there is obtained by precipitation an'd dryingawhite powder-of 'melting'pointV238-240" IC; Instead of monoacetylbenzidine there may be used any 7 other monoacyl'fdiamino diphenyl-compound,

such; has imonoformylbenzidine, monobenzoyl ben'zijdine .orfthe-iike; a j V r of monoajcetyl-ortho-,ortho etolidine,V

made by: monoacet'ylating ortho-ortho tolidine,

In this group those are again 'valua'ble' dyestuffs in which Ra'stands for CH3, i. e dye- I stuffs deriving from condensation products from 'ethyl 'acetoacetate'." JFo'r carrying out'th'eprocess there Ymay' be" used. quiteiigenerallyr diazo-comis continued for 600 parts of chlorobenzene and 2 parts of 'dif' ethylaniline, are heated together to boiling in a closed apparatus having a reflux condenser, while stirring. After distilling of aboutIlOO parts of chlorobenzene, parts of ethylaceto-ace- 'tate'are dropped into the mass in the course of 7 about half-an-hourand afew drops of diethylaniline are mixediinto the mass, which is then 7 V boiled feebly for 2- 3 hours and then cooled. The -mixture is then distilled with'steam 'tovremove" the chlorobenzene.

Theresidue is dissolved in dilute'caustic soda 7 solution and the solution is filtered. Addition of acid to the filtrate precipitates a white powder of 'melting point 222-223 C. which; in caustic soda solution, coupleswith one equivale'nt of a 'diazonium compound. 7 7

By condensing first one equivalent of the diamine with one equivalent of ethylacetoacetate and-then acylating the free aminogrouorlike products areobtained. V v

v V was s 25.3 parts of ortho-ortho-dichlorobenzidineV 1 and 200 parts of xylene .are'heated together,

7 while stirring, to feeble boiling in a closed appa; 1 ratushaving a reflux condenser. "ering of the temperature thereare added iby drops, in the course. of half-an-hour, 715 parts is "of ethyl acetoacetate mixed with 50 parts of 7 Without low xylene, and the mixture is keptfor about halfan-hour feebly boiling; it is then cooled to about 60 C. and at this temperature mixed with 12.2 parts of acetic anhydride and finally stirred for about half-ah-hoiir'While at 60 C.' Further :procedure is as describedin Example 2, whereby there is obta'ined a' white powder of melting point .l8-3-185 C; a

:A like product is obtained by condensing monoacetyl-ortho ortho-dichlorobenzidine with 'ethylacetoacetate, as described in Example 2."

V Examplev 4 '0 f 16.1 parts of 2:5-dichloraniline are dia zotiz ed "in 'the usualfmannerand introduced into a solu- 'tion of 33.8 parts of para actyl-para'-aceto-' "acetyl-ortho-ortho'-tolidide, 100' parts of caustic a V soda solution of 30 per cent strength and15 parts of calcined sodium carbonate in 2000 parts of water. 'The dyestufi is immediately precipitated.

It is filtered and dried; The formula of thenew Q ottonyarn isiimpregnated with a grounding liquor made by dissolving 3 parts'of para-acetyle paraiacetoacetyl-ortho-orthpfitolidide in ,300

parts 'of hotwater with the addition of 10 parts ot 7 sodium hydroxide solution of 30 per c ent; strength and 10 parts of Turkey red oil, there being also present sodiumchloride'or sodium sullfate, and making up the whole to 1 litre. The

yarn is wrung lout anddeveloped in a .diazosolution, buffered with sodium acetate and acidi fled with acetic vacid, correspondingfwithfl "parts -of 1-amino-2-methy1-4-chlorobenzene. There-is produced a'pure greenish yellow of .v'ery;:go0'd -fastness to washing, chlorine and keireboiling.

The formula. of the new dyestufifis 01150 ONHQONHOOoHG 0 on;

The grounding may occur at a higher temperature, for example at 80 'C.; .such arylides may .Diazo-compound from Coupled with Shade (2) 4-c111oro-2-i1itrani1ine 4-ch10ro-2-aminodipheny1ethe 4, 4-dichloro-2-aminodiphenyleth An 838v 1-amino-2-methyl-4-ehlorob me 1-amino-2-nitro-4-methylbenzene 8) 2, 5-dich1oraniline;

4, 2'-dichloro-2-aminodiphenylether (6) 1-amino-2-methoxy4-nitrobenzene 1-amino-2-nitro-4-methylbenzene Ethylester of 2-amino4'-cliJom-1, '1' diphenyl-sulfone-i-carb oxylic -aoi d. Ortho-chloraniline l Ortho-chloraniline 4-chloro-2-nitraniline 4-oh1oro-2-amino diphenylether 4, 4-dich1oto-2-aminodi phenylether- 4, 2-dichloro-2-aminodiphenylether 4 V 1-amino-2 methoxy-4-nitrobenzene-.

Ethylester of 2-amino4- ch1oro- 1, .1- diphenyl-sulfoneA-carboxylic acid.

Pata-acetyl-parM-acetoacetyl-ortho-ortho'- tolidide Pare-acetyl-para-acetoacetyl-ortho-ortho dighlorobenzidide.

4 Gi'een yellow.

Orange.

- Oran Yellow-orange.

Green-yellow.

Orange.

G reenish-yellow.

Yellow.

' Green-yellow.

(19) 2, 5-dichloraniline "PaIe-ae'etyl-p cetoacetylbeuzidide D (20) l-amino-Z-methoxy Pani gggtyl-para -acetoacetyl-ortho-ortho'- Do.

(21) Anthranilic acid-methylester. Do. (22) Anthtanilic acid-ethylester Do. a-Aminoanthraquinone Do.

(24) B-Naphthy1amine. D0.

5) l-chloro-Z-naphthyl Do. r (26) a-Naphthylamine .Reddish-yQellow. (27) Aminoazobenzena Orange yellow.

The dyestuffs 1, 4, 6, 20 and 22 of the foregoing v V 2 table correspond with the following formulae:-

CH 7. A. .l v a xzzyomeoua 1 OHQOONH NHoooHcoom if "N 'CHI Q What I claim is 2- 1 The monazo dyestuffs the general formula nlfii mi -r -cn-c -nl in which R1 represents a radical of the group consisting of alkyl radicals and aryl radicals of the benzene series, R2 a radical of an aromatic .4,4 -diamino-compound of the diphenyl series, R; a radical of the group consisting of alkyl radicals and aryl radicals of the benzene series, and R4 the radical of such a diazo-compound which contains no group promoting solubility, which prodnets are yellow powders dissolving in pyridine to green-yellow to orange and in sulfuric acid to green-yellow to scarlet solutions, and dyeing the vegetable fiber fast yellow tints.

2. The 'monoazo dyestuffs of the general formula in'which'Rs represents a radical-of the group consisting of alkyl radicals and aryl' radicals of the benzene series, R273, radical of an aromatic 4,4y-dia'mino-conipound of the diphenyl series, R3 a radical of the group consisting of alkyl radicals and aryl radicals of 'the benzene series, and R4 I the radical of such a diam-compound of the benzene series which contains no group promoting solubility, which products are yellow powders dissolving in pyridine to: green-yellow. to orange] and in sulfuric acid to green-yellow toscarlet solutions, and dyeing the vegetable fiber fast.

1 yellow tints.

3. The monoazo dyestuffs of the general formula v. nl-r lf-arlf-r i-ion-o 'rii i. v, V 0 H H 0 0 in which R1 represents an alkyl radical, R2 a" *radical of an aromatic 4,4'-diamino-compound of the diphenylseries, Rzra radical of the group consisting of alkyl radicals and .aryl radicals of r the benzene series, and R4 the radical of such a dia zo-compound of the benzene series which contains no group'promoting solubility, which prod- V nets are yellow powders dissolving in pyridine to green-yellow to orange andinfsulfuric acid to V green-yellow to scarlet solutions, and dyeing the vegetable fiber fast yellow tints. V V

4. The monoazo dyestufis' of the general formula r H 7 V in which Ri represents an alkyl radical containing not more than 3 carbon atoms, R2 a radical of in which R2 represents a radical of an aromatic 'o'Hlf (om (F l ,1 Hi we '2,o4a,sc9

an aromatic 4,4'-'diamino-compound of the m phenyl. series, R3 a radical of the group consisting of alkyl radicals and aryljradicals of the ben- 4,4'gdiamino-co-mpound of the diphenyl s'eries,Ra

a radicalof the group consisting of alkyl radicals and aryl radicalsof the benzene series, and R4 the radical of such a diazo-compound of the benzene series which contains no group promoting solubility, which products are yellow powders dis- 'solviiig'in' pyridine to green-yellow to orange and in sulfuric acidlto green-yellow to scarlet solu- V tions; and dyeing the vegetable fiber fast yellow tints. s a

6. The monoazo dyestuffs of the general formula I e V cm CH3 0 H l in which R represents the radical of a diazo compound of the benzene series containing neither sulfo groups nor carboxyl groups, which products are yellow powders dissolving in pyridine V to orange to green-yellowsolutions and in sulfuric acid to green-yellow to scarlet solutions,and dyeing vegetable fibers fast yellow tints.

, .7. The dyestuff of the formula H O CH:

which product is a" yellow powder dissolving in' pyridine to anorange solution and in sulfuric acid to a-brown-orange solution, and'dyeing the vegetable fiber fast yellow tints. V r V 1 8. The dyestuffs of the general formula on; on,

I I'OHO I it C O Oalkyl which products are yellow powders dissolving in pyridine'to green-yellow solutions and in sulfuric acid to green-yellow solutions, and dyeing the vegetable fiber fast yellow tints.

9. The dyestufi of the formula.

CH3 CH: O H l I COOCH:

which product is a yellow powder dissolving in pyridine to a green-yellow solution and in sulfuric acid to a green-yellow solution, and dyeing the vegetable fiber fast yellow tints.

10. The dy'stufi of the fdriiiulai MAX SCHMID. 15

D I SO LAI M E R 2,043,869. Max Schmid, Riehen, near Basel, Switzerland. MONOAZO DYESTUFES.

Pafient dated J une 9, 1936. Disclaimer filed March 23, 1939, by the asslgnee, Society of Chemical Industry in Basie.

Hereby disclaims claim 7; and

Hereby disclaims from the scope of claims 1, 2, 3, 4, 5, and 6 the dyestuff of the formula- CH; CH:

H (ilCHa 

